WO2017192689A1 - Copolymères à base d'acryloyle, terpolymères et leur utilisation en tant qu'inhibiteurs d'hydrates - Google Patents

Copolymères à base d'acryloyle, terpolymères et leur utilisation en tant qu'inhibiteurs d'hydrates Download PDF

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WO2017192689A1
WO2017192689A1 PCT/US2017/030795 US2017030795W WO2017192689A1 WO 2017192689 A1 WO2017192689 A1 WO 2017192689A1 US 2017030795 W US2017030795 W US 2017030795W WO 2017192689 A1 WO2017192689 A1 WO 2017192689A1
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Prior art keywords
divalent
chosen
groups
linear
copolymer
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Inventor
Mohamed Elanany
Abdullah AL-MALKI
Manal Al-Eid
Mohammed AL-DAOUS
Shaikh Asrof Ali
Khalid MAJNOUNI
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Saudi Arabian Oil Co
King Fahd University of Petroleum and Minerals
Aramco Services Co
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Saudi Arabian Oil Co
King Fahd University of Petroleum and Minerals
Aramco Services Co
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Priority to JP2018557909A priority Critical patent/JP6878463B2/ja
Priority to KR1020187035324A priority patent/KR102337330B1/ko
Priority to SG11201809667VA priority patent/SG11201809667VA/en
Priority to EP17723838.3A priority patent/EP3452526B1/fr
Priority to CN201780027848.5A priority patent/CN109071729B/zh
Publication of WO2017192689A1 publication Critical patent/WO2017192689A1/fr
Priority to SA522441290A priority patent/SA522441290B1/ar
Priority to SA518400351A priority patent/SA518400351B1/ar
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a heterocyclic ring containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/107—Limiting or prohibiting hydrate formation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/22—Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/32—Anticorrosion additives

Definitions

  • the present disclosure generally relates to acryloyl-based copolymers and terpolymers, to methods for synthesizing copolymers and terpolymers, and to methods for inhibiting formation of clathrate hydrates.
  • THIs thermodynamic hydrate inhibitors
  • Ethylene glycol that is, monoethylene glycol or MEG
  • methanol are examples of THIs.
  • LDHIs low dose hydrate inhibitors
  • LDHIs low dose hydrate inhibitors
  • LDHIs may interact with clathrate hydrate nuclei during early formation of clathrate hydrates.
  • inhibiting clathrate hydrate growth LDHIs may inhibit clathrate hydrate growth by binding to a surface of the clathrate hydrate.
  • Poly(N-vinylcaprolactam) and poly(N-methyl-N-vinylacetamide) are examples of LDHIs.
  • a third type of commercially available clathrate hydrate inhibitors are anti-agglomerates (that is, AAs), which act to inhibit clathrate hydrate agglomeration.
  • AAs may inhibit clathrate hydrate agglomeration by adsorbing to clathrate hydrates to prevent massive accumulation of clathrate hydrates.
  • AAs may inhibit clathrate hydrate agglomeration such that clathrate hydrates are kept in the form of a suspension.
  • Examples of AAs are anti-agglomerates based on quaternary ammonium cations.
  • THIs have been replaced by commercially available LDHIs, because THIs are viewed as being difficult to separate from pipeline fluids, are harmful to the environment, and require high concentrations to be effective.
  • commercially available LDHIs are also imperfect in that some are inefficient or incompatible with other additives, for example, corrosion inhibitors.
  • commercially available LDHIs which are capable of inhibiting clathrate hydrates having a structure (Type) I (that is, SI) crystalline structure under severe conditions, for example, extreme subcooling temperatures and pressure, are limited.
  • commercially available LDHIs, which are capable of inhibiting clathrate hydrates having a SI crystalline structure are limited to a narrow subcooling temperature range.
  • AAs are imperfect in that they fail to inhibit formation of clathrate hydrates.
  • Embodiments of the present disclosure are directed to copolymers and terpolymers having General Formula (I):
  • R 1 and R 3 are each independently chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups, optionally substituted with one or more Ci-C 6 aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof, where: the divalent C 4 -C 7 heteroaliphatic groups of R 1 and R 3 include one or two heteroatoms independently chosen from
  • R 1 or R3 O, N, and S, and the maximum number of heteroatoms in R 1 or R3 is two; R 2 is chosen from Q 1 and Q 2 :
  • R 4 and R 5 are each independently chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups, optionally substituted with one or more Ci-C 6 aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof, where: the divalent C 4 -C 7 heteroaliphatic groups of R 4 and R 5 include one or two heteroatoms independently chosen from O, N, and S, and the maximum number of heteroatoms in R 4 or R 5 is two; x is a molar fraction range chosen from 0.1 to 0.9; y is a molar fraction range chosen from 0.1 to 0.9; and z is a molar fraction range chosen from 0 to 0.8, where the summation of x, y, and z equals 1.
  • Embodiments of the present disclosure are also directed to methods for inhibiting formation of clathrate hydrates in a fluid capable of forming the clathrate hydrates, the method including: contacting the fluid with at least one copolymer or terpolymer of General Formula (I) under conditions suitable for forming the clathrate hydrates:
  • R 1 and R 3 are each independently chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups, optionally substituted with one or more Ci-C 6 aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof, where: the divalent C 4 -C 7 heteroaliphatic groups of R 1 and R 3 include one or two heteroatoms independently chosen from O, N, and S, and the maximum number of heteroatoms in R 1 or R 3 is two; R 2 is chosen from Q 1 and Q2 :
  • R 4 and R 5 are each independently chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups, optionally substituted with one or more Ci-C 6 aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof, where: the divalent C 4 -C 7 heteroaliphatic groups of R 4 and R 5 include one or two heteroatoms independently chosen from O, N, and S, and the maximum number of heteroatoms in R 4 or R 5 is two; x is a molar fraction range chosen from 0.1 to 0.9; y is a molar fraction range chosen from 0.1 to 0.9; and z is a molar fraction range chosen from 0 to 0.8, where the summation of x, y, and z equals 1.
  • FIG. 1 is a schematic depicting an offshore tie-in-platform in fluidic communication with wellheads and with an onshore plant via pipelines, where the tie-in -platform includes a receptacle for holding clathrate hydrate inhibitors;
  • FIG. 4 is a graph of Time (Minutes) with respect to Pressure (Bar) of Brine and a graph of Time (Minutes) with respect to Temperature (degrees Celsius, that is °C) of Rocking Cells RC-5 (that is, RC Temp), where the Temperature (°C) of the Rocking Cells RC-5 is programmed to change in three stages in accordance with the Starting Temperature (°C), Average Ramp (°C/minute) and Duration (Hours) as set forth in Table 4;
  • FIG. 5 is a graph of Time (Minutes, that is Min) with respect to Pressure (Bars) of acryloyl-based bipolymers having structure (ABB-1) (that is, KHI-5), (ABB-2) (that is, KHI-7), (ABB -3) (that is, KHI-8), and (ABB -4) (that is, KHI-9) as disclosed in Table 1 and of acryloyl- based terpolymers having structure (ABT-10) (that is, KHI-6) as disclosed in Table 1, and a graph of Time (Min) with respect to Temperature (°C) of the Rocking Cells RC-5 (that is, Temperature), where the Temperature (°C) of the Rocking Cells RC-5 is programmed to change in three stages in accordance with the Starting Temperature (°C), Average Ramp (°C/minute) and Duration (Hours) as set forth in Table 4;
  • FIG. 6 is a graph of Time (Min) with respect to Pressure (Bars) of acryloyl-based bipolymers having structure (ABB-5) (that is, KHI-10), (ABB-6) (that is, KHI-12), (ABB -7) (KHI-13), and (ABB-8) (that is, KHI-11) as disclosed in Table 1 and of polyvinylcaprolactam (that is, KHI-14), and a graph of Time (Min) with respect to Temperature (°C) of the Rocking Cells RC-5 (that is, Temperature), where the Temperature (°C) of the Rocking Cells RC-5 is programmed to change in three stages in accordance with the Starting Temperature (°C), Average Ramp (°C/minute) and Duration (Hour) as set forth in Table 4;
  • FIG. 7 is a graph of Time (Min) with respect to Pressure (Bars) of acryloyl-based bipolymers having structure (ABB-9) (that is, KHI-16) and of acryloyl-based terpolymers having structure (ABB-15) (that is, KHI-15) as disclosed in Table 1, and a graph of Time (Min) with respect to Temperature (°C) of the Rocking Cells RC-5 (that is, Temperature), where the Temperature (°C) of the Rocking Cells RC-5 is programmed to change in three stages in accordance with the Starting Temperature (°C), Average Ramp (°C/minute) and Duration (Hours) as set forth in Table 4; and
  • FIG. 8 is a graph of Duration (Min) with respect to Pressure (Bars) of acryloyl-based homopolymers having structure (ABH-11) (that is, KHI-1), (ABH-12) (that is, KHI-2), (ABH-13) (that is, KHI-3), and (ABH-14) (that is, KHI-4), and a graph of Duration (Min) with respect to Temperature (°C) of the Rocking Cells RC-5 (that is, RC Temp), where the Temperature (°C) of the Rocking Cells RC-5 is programmed to change in three stages in accordance with the Starting Temperature (°C), Average Ramp (°C/minute) and Duration (Hours) as set forth in Table 4.
  • copolymer refers to a polymer having two or more different monomeric repeating units.
  • the copolymer may include two different monomeric repeating units (that is, a bipolymer).
  • the copolymer may include three different monomeric repeating units (that is, a terpolymer).
  • the copolymers are random.
  • the copolymers are random when the distribution of monomeric repeating units follows statistical laws. For example, copolymers are random when the probability of finding a given monomeric repeating unit at a particular point in the polymer chain is equal to the mole fraction of that monomeric repeating unit in the chain. Random copolymers may also be referred to as statistical copolymers.
  • the term "monovalent” refers to a radical having an unsatisfied valence of one, where a valence "-" is unsatisfied at one end of the radical.
  • a hydrocarbon group is present at one end of an aliphatic radical or a heteroaliphatic radical
  • the aliphatic radical or the heteroaliphatic radical is monovalent when one hydrogen atom has been removed from the hydrocarbon group present at one end of the aliphatic radical or the heteroaliphatic radical.
  • the heteroaliphatic radical is monovalent when the heteroatom present at one end of the heteroaliphatic radical has an unsatisfied valence
  • divalent refers to a radical having an unsatisfied valence of two, where a valence "-" is unsatisfied at two ends of the radical.
  • a valence "-" is unsatisfied at two ends of the radical.
  • the aliphatic radical or the heteroaliphatic radical is divalent when one hydrogen atom has been removed from each of the hydrocarbon groups present at two ends of the aliphatic radical or the heteroaliphatic radical.
  • the heteroaliphatic radical is divalent when each of the heteroatoms present at two ends of the heteroaliphatic radical has an unsatisfied valence
  • the heteroaliphatic radical is divalent when one hydrogen atom has been removed from the hydrocarbon group present at one end of the heteroaliphatic radical and when the heteroatom present at one end of the heteroaliphatic radical has an unsatisfied valence
  • aliphatic refers to saturated straight chain (that is, linear or unbranched) and branched hydrocarbon radicals.
  • the aliphatic hydrocarbon radicals are monovalent or divalent.
  • alkyl includes straight and branched alkyl groups.
  • lower alkyl may be used to indicate alkyl groups (branched or unbranched) having from 1 to 6 carbon atoms.
  • the alkyl groups described contain from 1 to 7 aliphatic carbon atoms. In other embodiments, the alkyl groups described contain from 1 to 5 aliphatic carbon atoms. In still other embodiments, the alkyl groups described contain from 1 to 3 aliphatic carbon atoms.
  • Illustrative aliphatic groups thus include, but are not limited to, for example, methyl, ethyl, ⁇ -propyl, isopropyl, allyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, ie/t-pentyl, n-hexyl, sec-hexyl, moieties and the like.
  • heteroaliphatic refers to aliphatic radicals in which one or more carbon atoms in the main chain have been substituted with a heteroatom.
  • an aliphatic radical having four main chain atoms where one carbon atom has been substituted with one heteroatom is referred to as a C 4 heteroaliphatic.
  • an aliphatic radical having seven main chain atoms where two carbon atoms have been substituted with two heteroatoms is referred to as a C 7 heteroaliphatic.
  • the heteroaliphatic radicals are monovalent or divalent.
  • heteroaliphatic is intended to include aliphatic chains which contain one or more oxygen, sulfur, or nitrogen atoms, for example, in place of carbon atoms.
  • Heteroaliphatic moieties may be linear or branched.
  • heterocycloalkyl refers to radicals that combine the properties of heteroaliphatic and cyclic moieties and include, but are not limited to, saturated mono- or polycyclic ring systems having from 5 to 8 atoms, where at least one ring atom is a N heteroatom; and where zero, one or two ring atoms are additional heteroatoms independently chosen from S, O, and N (where the nitrogen and sulfur heteroatoms may optionally be oxidized).
  • heterocycloalkyl, heterocycle or heterocyclic refer to non-aromatic 5-membered, 6-membered, or 7-membered rings or polycyclic moieties where at least one ring atom is a N heteroatom, and where zero, one or two ring atoms are additional heteroatoms independently chosen from S, O, and N (where the nitrogen and sulfur heteroatoms may optionally be oxidized and the nitrogen atom may be quarternized) including, but not limited to, bicyclic or tricyclic groups.
  • heterocycles include, but are not limited to, heterocycles such as pyrrolidinyl, pyrazolidinyl, imidazolidinyl, piperidinyl, piperazinyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiazolidinyl, isothiazolidinyl, dithiazolyl, dithiazolidinyl, and azepanyl.
  • heterocycles such as pyrrolidinyl, pyrazolidinyl, imidazolidinyl, piperidinyl, piperazinyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiazolidinyl, isothiazolidinyl, dithiazolyl, dithiazolidinyl, and azepanyl.
  • the heterocycloalkyls, heterocycles or heterocyclics are saturated mono- or polycyclic moieties having from 5 to 8 ring atoms of which one ring atom is N; and of which zero, one or two ring atoms are additional heteroatoms independently chosen from S, O, and N; and the remaining ring atoms are carbon, the radicals being joined to the rest of the molecule via a N ring atom, such as, for example, pyrollidinyl, pyrazolidinyl, imidazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiazolidinyl, and azepanyl.
  • clathrate hydrates refers to crystalline water-based solids in which host water molecules enclathrate gas guest molecules.
  • the clathrate hydrates may include a structure (Type) I (that is, SI), a structure (Type) II (that is, SII), or a structure (Type) H (that is, SH) crystalline structure.
  • clathrate hydrate inhibition includes, but should not be limited to, thermodynamically modifying the conditions at which clathrate hydrates form, kinetically delaying clathrate hydrate nucleation, dissolving clathrate hydrates, breaking up clathrate hydrates, or combination thereof.
  • clathrate hydrate inhibition may include the complete cessation of clathrate hydrate formation, where clathrate hydrate formation is entirely prevented.
  • the terms “formation”, “forming”, and “form” refer to any process in which host water molecules enclathrate gas guest molecules in a crystalline structure, in which clathrate hydrates grow, in which clathrate hydrates adhere, in which clathrate hydrates agglomerate, or combination thereof.
  • enclathrate refers to hydrogen bonding of host water molecules around gas guest molecules.
  • subcooling temperature and T sc refer to the difference between an operating temperature of a field gas and the three-phase equilibrium temperature of the clathrate hydrate of the field gas at 140 bars.
  • first subcooling temperature refers to the difference between an operating temperature of a field gas in a first operation stage and the three-phase equilibrium temperature.
  • first subcooling temperature is from about 0 °C to about 4.0 °C, or from about 0 °C to about 1.0 °C, or from about 1.0 °C to about 2.0 °C, or from about 2.0 °C to about 3.5 °C, or about 4.0 °C.
  • second subcooling temperature refers to the difference between an operating temperature of a field gas in a second operation stage and the three-phase equilibrium temperature.
  • the second subcooling temperature is from about 4.0 °C to about 5.6 °C, or from about 4.0 °C to about 4.6 °C, or from about 4.6 °C to about 5.0 °C, or from about 5.0 °C to about 5.6 °C, or about 5.6 °C.
  • the term "third subcooling temperature" refers to the difference between an operating temperature of a field gas in a third operation stage and the three-phase equilibrium temperature.
  • the third subcooling temperature is from about 5.6 °C to about 10.5 °C, or from about 5.6 °C to about 7.0 °C, or from about 7.0 °C to about 8.6 °C, or from about 8.6 °C to about 10.0 °C, or about 10.5 °C.
  • Embodiments of the present disclosure are directed toward acryloyl-based copolymers (that is, ABC) having General Formula (I), to methods for synthesizing acryloyl-based copolymers having General Formula (I), and to methods for inhibiting formation of clathrate hydrates using acryloyl-based copolymers having General Formula (I).
  • acryloyl-based copolymers having General Formula (I) will now be described in detail. Thereafter, embodiments of methods for synthesizing copolymers of General Formula (I) will be described. Then, methods for inhibiting formation of clathrate hydrates using acryloyl-based copolymers having General Formula (I) will be described with reference to FIG. 1.
  • the disclosure describes acryloyl-based copolymers having General Formula (I): H 2 - ⁇ H- ⁇ f-CH 2 - ⁇ H ) z
  • R 1 and R 3 are each independently chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups, optionally substituted with one or more Ci-C 6 aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof, where the divalent C 4 -C 7 heteroaliphatic groups of R 1 and R 3 include one or two heteroatoms independently chosen from O, N, and S, and the maximum number of heteroatoms in R 1 or R 3 is two.
  • R 2 is chosen from Q 1 and Q2 :
  • R 4 and R 5 are each independently chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups, optionally substituted with one or more Ci-C 6 aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof, where: the divalent C 4 -C 7 heteroaliphatic groups of R 4 and R 5 include one or two heteroatoms independently chosen from O, N, and S, and the maximum number of heteroatoms in R 4 or R 5 is two.
  • x is a molar fraction range chosen from about 0.1 to about 0.9
  • y is a molar fraction range chosen from about 0.1 to about 0.9
  • z is a molar fraction range chosen from 0 to about 0.8, where the summation of x, y, and z equals 1.
  • R 1 is chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups, optionally substituted with one or more Ci-C 6 aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof, where the divalent C 4 -C 7 heteroaliphatic groups of R 1 include one or two heteroatoms independently chosen from O, N, and S, and the maximum number of heteroatoms in R 1 is two.
  • R 1 is chosen from divalent C 4 -C 7 linear aliphatic groups, divalent C 4 -C 7 branched aliphatic groups, divalent C 4 -C 7 linear heteroaliphatic groups, and divalent C 4 -C 7 branched heteroaliphatic groups.
  • R 1 is chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups.
  • R 1 is chosen from divalent C 4 -C 6 linear heteroaliphatic groups.
  • R 1 is chosen from divalent C 4 -C 6 linear heteroaliphatic groups including one heteroatom, where the heteroatom is O.
  • R 1 is chosen from -(CH 2 ) 4 -, -(CH 2 ) 5 -, and -(CH 2 ) 2 -0-(CH 2 ) 2 -.
  • R 1 is optionally substituted with one or more substituting groups.
  • R 1 may include from 1 to 3 substituting groups.
  • the divalent C 4 -C 7 aliphatic groups and the divalent C 4 -C 7 heteroaliphatic groups include additional unsatisfied valences "-" within the divalent C 4 -C 7 aliphatic groups and the divalent C 4 -C 7 heteroaliphatic groups to accommodate bonding with the substituting groups.
  • R 1 is chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups and is substituted
  • additional hydrogen atoms may have been removed from the hydrocarbon groups present within the divalent C 4 -C 7 aliphatic groups and the divalent C 4 -C 7 heteroaliphatic groups to accommodate bonding with the substituting groups.
  • R 1 is optionally substituted with one or more Ci-C 6 aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof. In embodiments, R 1 is optionally substituted with one or more Ci-C 6 linear aliphatic groups, Ci-C 6 branched aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof. In embodiments, R 1 is substituted with one or more Ci-C 6 linear aliphatic groups, Ci-C 6 branched aliphatic groups, or combination thereof. In illustrative, non-limiting embodiments, R 1 is substituted with one or more lower alkyls.
  • R 1 is substituted with one or more C 1 -C 3 linear aliphatic groups, C 1 -C 3 branched aliphatic groups, or combination thereof. In still other illustrative, non-limiting embodiments, R 1 is substituted with one or more substituting groups independently chosen from methyl, ethyl, n-propyl, isopropyl, allyl moieties, or combination thereof.
  • R 1 is substituted with one or more heteroatoms independently chosen from O, N, and S.
  • the heteroatoms may form a single bond or a double bond with R 1 .
  • R 1 is substituted with one heteroatom chosen from O, N, and S.
  • R 1 is substituted with one heteroatom, where the one heteroatom is O.
  • R 1 is chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups
  • the C 4 -C 7 aliphatic groups and the C 4 -C 7 heteroaliphatic groups include an unsatisfied valence "-"at two ends.
  • R 1 forms a heterocycloalkyl or a heterocycle when bonded with the -N- in the rest of the copolymer molecule via its two unsatisfied end valences.
  • the heterocycloalkyl or heterocycle formed when R 1 is bonded with the -N- in the rest of the copolymer is non-aromatic.
  • the heterocycloalkyl or heterocycle formed is chosen from pyrollidinyl, pyrazolidinyl, imidazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiazolidinyl, and azepanyl.
  • the heterocycloalkyl, or heterocycle formed is chosen from pyrrolidinyl, piperidinyl, morpholinyl, and azepanyl.
  • the heterocycloalkyl or heterocycle formed when R 1 is bonded with the -N- in the rest of the copolymer molecule has the following structure:
  • heterocycloalkyl or heterocycle is attached to the rest of the copolymer
  • the is substituted.
  • R is chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups, optionally substituted with one or more Ci-C 6 aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof, where the divalent C 4 -C 7 heteroaliphatic groups of R include one or two heteroatoms independently chosen from O, N, and S, and the maximum number of heteroatoms in R is two.
  • R is chosen from divalent C 4 -C 7 linear aliphatic groups, divalent C 4 -C 7 branched aliphatic groups, divalent C 4 -C 7 linear heteroaliphatic groups, and divalent C 4 -C 7 branched heteroaliphatic groups.
  • R is chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups.
  • R is chosen from divalent C 4 -C 6 linear aliphatic groups.
  • R 3 is -(CH 2 ) 4 -.
  • R is optionally substituted with one or more substituting groups.
  • R 3 may include from 1 to 3 substituting groups.
  • the divalent C 4 -C 7 aliphatic groups and the divalent C 4 -C 7 heteroaliphatic groups include additional unsatisfied valences "-" within the divalent C 4 -C 7 aliphatic groups and the divalent C 4 -C 7 heteroaliphatic groups to accommodate bonding with the substituting groups.
  • R is chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups and is substituted
  • additional hydrogen atoms may have been removed from the hydrocarbon groups present within the divalent C 4 -C 7 aliphatic groups and the divalent C 4 -C 7 heteroaliphatic groups to accommodate bonding with the substituting groups.
  • R is optionally substituted with one or more Ci-C 6 aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof.
  • R is optionally substituted with one or more Ci-C 6 linear aliphatic groups, Ci-C 6 branched aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof.
  • R is substituted with one or more Ci-C 6 linear aliphatic groups, Ci-C 6 branched aliphatic groups, or combination thereof.
  • R is substituted with one or more lower alkyls.
  • R is substituted with one or more C 1 -C 3 linear aliphatic groups, C 1 -C 3 branched aliphatic groups, or combination thereof.
  • R is substituted with one or more substituting groups independently chosen from methyl, ethyl, n-propyl, isopropyl, allyl moieties, or combination thereof.
  • R is substituted with one or more heteroatoms independently chosen from O, N, and S.
  • the heteroatoms may form a single bond or a double bond with R 3.
  • R 3 is substituted with one heteroatom chosen from O, N, and S.
  • R is substituted with one heteroatom, where the one heteroatom is O.
  • the C 4 -C 7 aliphatic groups and the C 4 -C 7 heteroaliphatic groups include an unsatisfied valence "-"at two ends.
  • R forms a heterocycloalkyl or a heterocycle when bonded with the -N- in the rest of the copolymer molecule via its two unsatisfied end valences.
  • the heterocycloalkyl or heterocycle formed when R is bonded with the -N- in the rest of the copolymer is non-aromatic.
  • the heterocycloalkyl or heterocycle formed is chosen from pyrollidinyl, pyrazolidinyl, imidazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiazolidinyl, and azepanyl.
  • the heterocycloalkyl, or heterocycle formed is chosen from pyrrolidinyl, piperidinyl, morpholinyl, and azepanyl.
  • the heterocycloalkyl or heterocycle formed when R is bonded with the -N- in the rest of the copolymer molecule has the following structure:
  • the is substituted.
  • the is chosen from
  • R 2 is chosen from Q 1 and Q2 :
  • R 4 and R 5 are each independently chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups, optionally substituted with one or more Ci-C 6 aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof, where the divalent C 4 -C 7 heteroaliphatic groups of R 4 and R 5 include one or two heteroatoms independently chosen from O, N, and S, and the maximum number of heteroatoms in R 4 or R 5 is two.
  • R4 is chosen from divalent C 4 -C 7 linear aliphatic groups, divalent C 4 -C 7 branched aliphatic groups, divalent C 4 -C 7 linear heteroaliphatic groups, and divalent C 4 -C 7 branched heteroaliphatic groups.
  • R 4 is chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups.
  • R 4 is chosen from divalent C 4 -C 6 linear aliphatic groups.
  • R 4 is chosen from -(CH 2 ) 4 -, -(CH 2 )s-, and -(CH 2 ) 6 -.
  • R4 is optionally substituted with one or more substituting groups.
  • R 4 may include from 1 to 3 substituting groups.
  • the divalent C 4 -C 7 aliphatic groups and the divalent C 4 -C 7 heteroaliphatic groups include additional unsatisfied valences "-" within the divalent C 4 -C 7 aliphatic groups and the divalent C 4 -C 7 heteroaliphatic groups to accommodate bonding with the substituting groups.
  • R 4 is chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups and is substituted
  • additional hydrogen atoms may have been removed from the hydrocarbon groups present within the divalent C 4 -C 7 aliphatic groups and the divalent C 4 -C 7 heteroaliphatic groups to accommodate bonding with the substituting groups.
  • R4 is optionally substituted with one or more Ci-C 6 aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof.
  • R 4 is optionally substituted with one or more Ci-C 6 linear aliphatic groups, Ci-C 6 branched aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof.
  • R 4 is substituted with one or more Ci-C 6 linear aliphatic groups, Ci-C 6 branched aliphatic groups, or combination thereof.
  • R 4 is substituted with one or more lower alkyls.
  • R 4 is substituted with one or more C 1 -C 3 linear aliphatic groups, C 1 -C 3 branched aliphatic groups, or combination thereof. In still other illustrative, non-limiting embodiments, R 4 is substituted with one or more substituting groups independently chosen from methyl, ethyl, n -propyl, isopropyl, allyl moieties, or combination thereof.
  • R4 is substituted with one or more heteroatoms independently chosen from O, N, and S.
  • the heteroatoms may form a single bond or a double bond with R 4 .
  • R 4 is substituted with one heteroatom chosen from O, N, and S.
  • R 4 is substituted with one heteroatom, where the one heteroatom is O.
  • R 4 is chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups
  • the C 4 -C 7 aliphatic groups and the C 4 -C 7 heteroaliphatic groups include an unsatisfied valence "-"at two ends.
  • R 4 forms a heterocycloalkyl or a heterocycle when bonded with the -N- in the rest of the copolymer molecule via its two unsatisfied end valences.
  • the heterocycloalkyl or heterocycle formed when R 4 is bonded with the -N- in the rest of the copolymer is non-aromatic.
  • the heterocycloalkyl or heterocycle formed is chosen from pyrollidinyl, pyrazolidinyl, imidazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiazolidinyl, and azepanyl.
  • the heterocycloalkyl, or heterocycle formed is chosen from pyrrolidinyl, piperidinyl, morpholinyl, and azepanyl.
  • the heterocycloalkyl or heterocycle formed when R 4 is bonded with the -N- in the rest of the copolymer molecule has the following structure:
  • R 5 is chosen from divalent C 4 -C 7 linear aliphatic groups, divalent C 4 -C 7 branched aliphatic groups, divalent C 4 -C 7 linear heteroaliphatic groups, and divalent C 4 -C 7 branched heteroaliphatic groups.
  • R 5 is chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups.
  • R 5 is chosen from divalent C 4 -C 6 linear aliphatic groups.
  • R 5 is chosen from -(CH 2 )6- substituted with an O heteroatom.
  • R 5 is optionally substituted with one or more substituting groups.
  • R 5 may include from 1 to 3 substituting groups.
  • the divalent C 4 -C 7 aliphatic groups and the divalent C 4 -C 7 heteroaliphatic groups include additional unsatisfied valences "-" within the divalent C 4 -C 7 aliphatic groups and the divalent C 4 -C 7 heteroaliphatic groups to accommodate bonding with the substituting groups.
  • R 5 is chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups and is substituted
  • additional hydrogen atoms may have been removed from the hydrocarbon groups present within the divalent C 4 -C 7 aliphatic groups and the divalent C 4 -C 7 heteroaliphatic groups to accommodate bonding with the substituting groups.
  • R 5 is optionally substituted with one or more Ci-C 6 aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof.
  • R 5 is optionally substituted with one or more Ci-C 6 linear aliphatic groups, Ci-C 6 branched aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof.
  • R 5 is substituted with one or more Ci-C 6 linear aliphatic groups, Ci-C 6 branched aliphatic groups, or combination thereof.
  • R 5 is substituted with one or more lower alkyls.
  • R 5 is substituted with one or more C 1 -C 3 linear aliphatic groups, C 1 -C 3 branched aliphatic groups, or combination thereof. In still other illustrative, non-limiting embodiments, R 5 is substituted with one or more substituting groups independently chosen from methyl, ethyl, n -propyl, isopropyl, allyl moieties, or combination thereof.
  • R 5 is substituted with one or more heteroatoms independently chosen from O, N, and S.
  • the heteroatoms may form a single bond or a double bond with R 5 .
  • R 5 is substituted with one heteroatom chosen from O, N, and S.
  • R 5 is substituted with one heteroatom, where the one heteroatom is O.
  • R 5 is chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups
  • the C 4 -C 7 aliphatic groups and the C 4 -C 7 heteroaliphatic groups include an unsatisfied valence "-"at two ends.
  • R 5 forms a heterocycloalkyl or a heterocycle when bonded with the -N- in the rest of the copolymer molecule via its two unsatisfied end valences.
  • the heterocycloalkyl or heterocycle formed when R 5 is bonded with the -N- in the rest of the copolymer is non-aromatic.
  • the heterocycloalkyl or heterocycle formed is chosen from pyrollidinyl, pyrazolidinyl, imidazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiazolidinyl, and azepanyl.
  • the heterocycloalkyl, or heterocycle formed is chosen from pyrrolidinyl, piperidinyl, morpholinyl, and azepanyl.
  • the heterocycloalkyl or heterocycle formed when R 5 is bonded with the -N- in the rest of the copolymer molecule has the following structure:
  • heterocycloalkyl or heterocycle is attached to the rest of the copolymer
  • the is substituted.
  • the is and is chosen from
  • x is a molar fraction range chosen from about 0.1 to about 0.9; y is a molar fraction range chosen from about 0.1 to about 0.9; and z is a molar fraction range chosen from 0 to about 0.8.
  • x is a molar fraction range chosen from about 0.1 to about 0.9, from about 0.25 to about 0.75, or from about 0.33 to about 0.66, or a molar fraction of about 0.5.
  • x is a molar fraction of greater than 0.
  • y is a molar fraction range chosen from about 0.1 to about 0.9, or from about 0.25 to about 0.75, or from about 0.33 to about 0.66, or a molar fraction of about 0.5. In illustrative, non-limiting embodiments, y is a molar fraction of greater than 0. In embodiments, z is a molar fraction range chosen from 0 to about 0.8, or from about 0.25 to about 0.5, or a molar fraction of about 0.33. In embodiments, z is a molar fraction of greater than 0. In the copolymers of General Formula (I), the summation of x, y and z equals 1. In embodiments, x and y are equimolar fractions. In other embodiments, x, y, and z are equimolar fractions.
  • the viscosity average molecular weight of the copolymers of General Formula (I) is from about 500 grams/mole (that is g/mol) to about 1,000,000 g/mol, or from about 750 g/mol to about 500,000 g/mol, or from about 1,000 g/mol to about 100,000 g/mol, or from about 2,500 g/mol to about 20,000 g/mol.
  • the viscosity average molecular weight of the copolymers was determined via gel permeation chromatography (that is, GPC), employing 0.7% trimethylamine in tetrahydrofuran (that is, THF) as a mobile phase, PhenogelTM (Phenomenex, Sutter Creek, CA) as stationary phases (of differing pore sizes, 500 A, 100 A, and 50 A) in three columns in series, with a refractive index detector (that is, RID). Calibration was performed using polystyrene standards. Moreover, the viscosity average molecular weight of the copolymers of General Formula (I) as determined by GPC was confirmed via sulfur elemental analysis.
  • GPC gel permeation chromatography
  • the viscosity average molecular weight of the copolymers of General Formula (I) is from about 500 g/mol to about 1,000,000 g/mol. In alternative illustrative, non-limiting embodiments, the viscosity average molecular weight of the copolymers of General Formula (I) is from about 500 g/mol to about 20,000 g/mol.
  • R 4 and R 5 are each independently chosen from divalent C 4 -C 6 linear aliphatic groups, and R 4 and R 5 are substituted with one or more C1-C3 aliphatic groups.
  • R 2 is Q 1
  • R 4 is chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups.
  • R 2 is Q 2
  • R 5 is chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups.
  • R 2 is Q 1 , and R 4 is chosen from divalent C 4 -C 6 linear aliphatic groups.
  • R 2 is Q 2
  • R 5 is chosen from divalent C 4 -C 6 linear aliphatic groups.
  • R 2 is Q 2
  • R 5 is chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups, and R 5 is substituted with one heteroatom independently chosen from O, N, and S.
  • R 1 is chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups
  • R is chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups
  • R 4 and R 5 are each independently chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups
  • x is a molar fraction range of from about 0.25 to about 0.75
  • z is a molar fraction range of from about 0.25 to about 0.5.
  • x is a molar fraction range of from about 0.25 to about 0.75
  • y is a molar fraction range of from about 0.25 to about 0.75
  • z is a molar fraction range of from about 0.25 to about 0.5.
  • the at least one copolymer of General Formula (I) is water soluble. In further embodiments, the at least one copolymer of General Formula (I) is thermally stable. In illustrative, non-limiting embodiments, the at least one copolymer of General Formula (I) is thermally stable up to a temperature of about 50 °C.
  • the disclosure describes methods for synthesizing the copolymers of General Formula (I).
  • the copolymers of General Formula (I) may be synthesized via any suitable synthetic scheme known to a person of ordinary skill in the art.
  • the methods for synthesizing the copolymers of General Formula (I) include providing 4,4-Azobis(4- cyanovaleric acid) (that is, ABCVA) (about 1.25 millimole, that is mmol) with a solution having monomeric repeating units having formula (la) (about 24 mmol), (lb) (about 24 mmol), and (lc) (about 18 mmol):
  • reaction mixture is stirred under N 2 at about 63 °C using a magnetic stir-bar for 24 hours to obtain a reaction product including a synthesized acryloyl-based terpolymer. After 24 hours, in embodiments, the reaction product is cooled to room temperature, washed with petroleum ether (about 3x20 mL), and freeze-dried.
  • the methods for synthesizing the copolymers of General Formula (I) include providing ABCVA (about 1.25 mmol) with a solution having monomeric repeating units having formula (la) (about 24 mmol), (Id) (about 24 mmol), and (lc) (about 18 mmol):
  • reaction mixture is stirred under N 2 at about 63 °C using a magnetic stir-bar for 24 hours to obtain a reaction product including a synthesized acryloyl- based terpolymer.
  • the reaction product is homogenous, cooled to room temperature, washed with petroleum ether (about 3x20 mL), and freeze-dried.
  • R 1 , R 2 , R 3 , R 4 , and R 5 of General Formula (I) or of monomeric repeating units having formula (la), (lb), (lc), and (Id) are as described previously with regard to General Formula (I).
  • quantities of reactants, for example, monomeric repeating units (la), (lb), (lc), and (Id) in the solution may be adjusted to achieve varying molar fractions x, y, or z, of each monomeric repeating unit.
  • bipolymers and terpolymers may be synthesized via the methods described in this disclosure by adding only the monomeric repeating units (la), (lb), (lc), and (Id) which are desired in the copolymers of General Formula (I).
  • the disclosure describes methods for inhibiting clathrate hydrates in a fluid capable of forming the clathrate hydrates, the methods including contacting the fluid with at least one copolymer of General Formula (I) under conditions suitable for forming clathrate hydrates.
  • the at least one copolymer of General Formula (I) is as described previously.
  • R 1 and R 3 are each independently chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups, optionally substituted with one or more Ci-C 6 aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof, where the divalent C 4 -C 7 heteroaliphatic groups of R 1 and R 3 include one or two heteroatoms independently chosen from O, N, and S, and the maximum number of heteroatoms in R 1 or R3 is two.
  • R 2 is chosen from Q 1 and Q 2 :
  • R 4 and R 5 are each independently chosen from divalent C 4 -C 7 aliphatic groups and divalent C 4 -C 7 heteroaliphatic groups, optionally substituted with one or more Ci-C 6 aliphatic groups, heteroatoms independently chosen from O, N, and S, or combination thereof, where: the divalent C 4 -C 7 heteroaliphatic groups of R 4 and R 5 include one or two heteroatoms independently chosen from O, N, and S, and the maximum number of heteroatoms in R 4 or R 5 is two.
  • x is a molar fraction range chosen from about 0.1 to about 0.9
  • y is a molar fraction range chosen from about 0.1 to about 0.9
  • z is a molar fraction range chosen from 0 to about 0.8, where the summation of x, y, and z equals 1.
  • R 1 is chosen from divalent linear C 4 -C 6 aliphatic groups and divalent linear C 4 -C 6 heteroaliphatic groups
  • R 2 is Q 2
  • R 5 is chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups.
  • R 1 is chosen from divalent linear C 4 -C 6 aliphatic groups and divalent linear C 4 -C 6 heteroaliphatic groups
  • R 2 is Q 1
  • R 4 is chosen from divalent C 4 -Cs linear aliphatic groups and divalent C 4 -Cs linear heteroaliphatic groups.
  • R 1 is chosen from divalent linear C 4 -C 6 aliphatic groups and divalent linear C 4 -C 6 heteroaliphatic groups
  • R 4 and R 5 are each independently chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups
  • x is a molar fraction of about 0.8
  • y is a molar fraction of about 0.2.
  • R 1 is chosen from divalent C 4 -Cs linear aliphatic groups and divalent C 4 -Cs linear heteroaliphatic groups.
  • R 4 and R 5 are each independently chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups.
  • R 1 is chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups
  • R is chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups
  • R 4 and R 5 are each independently chosen from divalent C 4 -C 6 linear aliphatic groups and divalent C 4 -C 6 linear heteroaliphatic groups
  • x is a molar fraction range of from about 0.25 to about 0.75
  • y is a molar fraction range of from about 0.25 to about 0.75
  • z is a molar fraction greater than 0.
  • x and y are equimolar fractions.
  • x, y, and z are equimolar fractions.
  • the viscosity average molecular weight of the at least one copolymer is in the range of from about 500 g/mol to about 20,000 g/mol.
  • the fluid is contacted with a formulation including the at least one copolymer of General Formula (I).
  • the fluid is contacted with about 3 weight % of the formulation, where the amount of formulation relates to the percentage of the water cut.
  • the formulation includes one or more of the at least one copolymer of General Formula (I) (for example, two or more copolymers of General Formula (I) could be used), solvents, or additives.
  • the at least one copolymer of General Formula (I) is compatible with additives.
  • the additives are chosen from corrosion inhibitors and synergists.
  • the formulation includes from about 0.01 weight % to about 33 weight % of the at least one copolymer of General Formula (I), from 0 weight % to about 67 weight % of the solvent, and from 0 weight % to about 1 weight % of the additive.
  • the formulation includes from about 0.1 weight % to about 5 weight % of the at least one copolymer of General Formula (I), from 0 weight % to about 20 weight % of the solvent, from 0 weight % to about 10 weight % of the additives, from 0 parts per million (that is, ppm; a mass fraction) to about 3000 ppm of the corrosion inhibitors, from 0 ppm to about 3000 ppm of the scale inhibitors, from 0 weight % to about 40 weight % of the thermodynamic hydrate inhibitors, and from about 0 weight % to about 10 weight % of the anti-agglomerates.
  • the amounts disclosed of the formulation relate to the percentage or ppm of the water cut.
  • the solvents are chosen from water, alcohols, for example, monoethylene glycol, methanol, ethanol, and isobutanol, ketones, ethers, and non- polar aromatics, for example, toluene and benzene.
  • the solvents are alcohols chosen from glycols, for example, monoethylene glycol.
  • the additives are chosen from corrosion inhibitors and synergists.
  • the corrosion inhibitors include gas corrosion inhibitors.
  • the synergists are chosen from scale inhibitors, thermodynamic hydrate inhibitors, low dose hydrate inhibitors, and anti- agglomerates.
  • the thermodynamic hydrate inhibitors are chosen from glycol ethers and methanol.
  • low dose hydrate inhibitors are chosen from Poly(N-vinylcaprolactam) and poly(N-methyl-N- vinylacetamide).
  • the fluid is contacted with at least one copolymer of General Formula (I) under conditions suitable for forming clathrate hydrates.
  • the at least one copolymer of General Formula (I) is contacted with the fluid via methods known to one of ordinary skill in the art.
  • the at least one copolymer of General Formula (I) may be contacted with the fluid via adding, combining, mixing, injecting, or combination thereof.
  • conditions suitable for forming clathrate hydrates include conditions where the pressure on the fluid is from about 11 bara to about 200 bara, or from about 11 bara to about 50 bara, or from about 50 bara to about 70 bara, or from about 70 bara to about 100 bara, or from about 100 bara to about 140 bara, or from about 140 bara to about 150 bara, or from about 150 bara to about 200 bara, and also includes conditions where the temperature of the fluid is from about 0 °C to about 25 °C, or from about 0 °C to about 10 °C, or from about 10 °C to about 12 °C, or from about 12 °C to about 16 °C, or from about 16 °C to about 19 °C, or from about 19 °C to about 20 °C, or from about 20 °C to about 25 °C.
  • conditions suitable for forming clathrate hydrates include conditions where the pressure on the fluid is from about 11 bara to about 200 bara, or from about 11 bara
  • contacting the fluid with at least one copolymer of General Formula (I) under conditions suitable for forming the clathrate hydrates is effective to inhibit or inhibits the formation of the clathrate hydrates at a first subcooling temperature. In other embodiments, contacting the fluid with at least one copolymer of General Formula (I) under conditions suitable for forming the clathrate hydrates is effective to inhibit or inhibits the formation of the clathrate hydrates at a second subcooling temperature.
  • contacting the fluid with at least one copolymer of General Formula (I) under conditions suitable for forming the clathrate hydrates is effective to inhibit or inhibits the formation of the clathrate hydrates at a third subcooling temperature.
  • contacting the fluid with at least one copolymer of General Formula (I) under conditions suitable for forming the clathrate hydrates is effective to inhibit or inhibits the formation of the clathrate hydrates in a pressure range of from about 40 bars to about 200 bars. In other illustrative, non-limiting embodiments, contacting the fluid with at least one copolymer of General Formula (I) under conditions suitable for forming the clathrate hydrates is effective to inhibit or inhibits the formation of the clathrate hydrates in a pressure range of from about 70 bars to about 100 bars.
  • the fluid capable of forming clathrate hydrates includes water host molecules and natural gas guest molecules.
  • the natural gas guest molecules are chosen from methane, ethane, propane, butane, pentane, carbon dioxide, hydrogen sulfide, nitrogen, or combination thereof.
  • the fluid capable of forming clathrate hydrates includes natural gas guest molecules in the following compositional amounts: methane (from about 60-90 mole %); ethane (from about 0-4 mole %); propane (from about 0-1 mole %); butane (from about 0-1 mole %); carbon dioxide (from about 5-15 mole %); hydrogen sulfide (from about 0-5 mole %); and nitrogen (from about 5-15 mole %).
  • the fluid capable of forming clathrate hydrates includes natural gas guest molecules in the following compositional amount: methane (about 79.6 mole %); ethane (about 1.4 mole %); propane (about 0.2 mole %); butane (about 0.1 mole %); carbon dioxide (about 9.2 mole %); hydrogen sulfide (about 2.3 mole %); and nitrogen (about 7.2 mole %).
  • the fluid capable of forming clathrate hydrates includes brine, such as is described subsequently in Table 2.
  • the brine includes chloride anions, sodium cations, acetic acid, formic acid, a conjugate base of acetic acid, a conjugate base of formic acid, or combination thereof.
  • the fluid capable of forming clathrate hydrates includes acid gas guest molecules.
  • the fluid capable of forming clathrate hydrates includes carbon dioxide and hydrogen sulfide.
  • the fluid capable of forming clathrate hydrates is rich in carbon dioxide, hydrogen sulfide, or a combination of carbon dioxide and hydrogen sulfide.
  • the fluid capable of forming clathrate hydrates may be rich in hydrogen sulfide where it includes at least about 2 mole % of hydrogen sulfide.
  • the fluid capable of forming clathrate hydrates may be rich in carbon dioxide where it includes at least about 8 mole % of carbon dioxide.
  • the fluid capable of forming clathrate hydrates may be rich in both carbon dioxide and hydrogen sulfide where it includes at least about 8 mole % of carbon dioxide and at least about 2 mole % of hydrogen sulfide.
  • the fluid capable of forming clathrate hydrates includes carbon dioxide, hydrogen sulfide, nitrogen, or combination thereof.
  • the fluid capable of forming clathrate hydrates includes methane, ethane, propane, butane, carbon dioxide, hydrogen sulfide, and nitrogen gas guest molecules. In yet still other illustrative, non-limiting embodiments, the fluid capable of forming clathrate hydrates does not include hydrogen sulfide, carbon dioxide, or a combination of hydrogen sulfide and carbon dioxide.
  • the fluid capable of forming clathrate hydrates is capable of forming SI clathrate hydrates, SII clathrate hydrates, SH clathrate hydrates, or combination thereof.
  • fluids capable of forming SI clathrate hydrates include at least one of methane, ethane, propane, butane, carbon dioxide, or hydrogen sulfide.
  • fluids capable of forming SII clathrate hydrates include at least one of propane, butane, or pentane.
  • SI clathrate hydrates and SII clathrate hydrates have crystalline cubic structures which are well known to one of ordinary skill in the art.
  • SH clathrate hydrates have hexagonal structures which are well known to one of ordinary skill in the art.
  • the contacting is effective to inhibit or inhibits formation of SI clathrate hydrates, SII clathrate hydrates, SH clathrate hydrates, or combination thereof.
  • the fluid is contacted with the at least one copolymer of General Formula (I) in an amount effective to inhibit clathrate hydrate formation.
  • the fluid is contacted with from about 0.01 weight % to about 33 weight %, or from about 0.1 weight % to about 4 weight %, or from about 0.5 weight % to about 4 weight %, or about 2.5 weight % of the at least one copolymer of General Formula I.
  • the weight % of the at least one copolymer of General Formula I refers to the weight % of the water cut.
  • the at least one copolymer of General Formula (I) is water soluble.
  • the fluid capable of forming the clathrate hydrates is contacted with the at least one copolymer of General Formula (I) at a tie-in-platform 10.
  • the tie-in-platform 10 is an offshore platform which is in fluidic communication with an onshore plant 100 via a pipeline 50.
  • the tie-in- platform 10 is in fluidic communication with wellheads 200, 300, 400, 500, and 600, which provide an interface for drilling and production equipment.
  • the fluid capable of forming the clathrate hydrates is flowing in pipeline 50.
  • the fluid capable of forming the clathrate hydrates is flowing in pipeline 50 from an offshore site to an onshore site.
  • the fluid capable of forming the clathrate hydrates is flowing in the pipeline 50 from the tie-in-platform 10 to the onshore plant 100.
  • the at least one copolymer of General Formula (I) is injected into the fluid capable of forming the clathrate hydrates at the tie-in-platform 10.
  • the tie-in-platform 10 includes a receptacle 15 for holding clathrate hydrate inhibitors and a clathrate hydrate inhibitor injection skid 20.
  • the at least one copolymer of General Formula (I) is held in the receptacle 15 for holding clathrate hydrate inhibitors.
  • the at least one copolymer of General Formula (I) is injected into the fluid capable of forming the clathrate hydrates via the clathrate hydrate inhibitor injection skid 20.
  • Acryloyl-based bipolymers that is, ABB having General Formula (I) in which R 1 is -(CH 2 ) 2 -0-(CH 2 )2-, R 2 is Q 1 in which R 4 is -(CH 2 ) 4 -, R 3 is not present, x is about 0.5, y is about 0.5, and z is 0, were synthesized.
  • acryloyl-based bipolymers having General Formula (I) were synthesized by adding ABCVA (about 350 milligrams, that is mg, 1.25 mmol) to a solution having a monomeric repeating unit of structure (Ml) (about 36.3 mmol):
  • acryloyl- based terpolymers having General Formula (I) were synthesized by adding ABCVA (about 0.35 g, 1.25 mmol) to a solution having a monomeric repeating unit of structure (Ml) (about 3.38 g, 24 mmol):
  • thioglycolic acid (about 0.995 g, 10.8 mmol) in water (about 42 mL) to form a reaction mixture.
  • the reaction mixture was kept under N 2 for 20 minutes.
  • the reaction mixture was heated under N 2 at about 63 °C for 24 hours. After 24 hours, the reaction mixture was cooled to room temperature to obtain a homogenous solution.
  • the reaction mixture was washed with petroleum ether (about 3x20 mL) to remove unreactive materials. A water layer was extracted and bubbled with N 2 to remove soluble ether from the reaction mixture.
  • the reaction mixture was freeze - dried to evaporate solvent and to obtain an acryloyl-based terpolymer of structure (ABT-10):
  • the terpolymer of structure (ABT-10) was confirmed via the spectra of FIGS. 2-3.
  • the number of protons associated with spectrum peaks can be estimated via integration thereof in FIG. 2; additionally, the formation of a polymer can be determined via the spectrum peaks in FIG. 2.
  • the functional groups of the terpolymer of structure (ABT-10) can be confirmed via chemical shifts in the spectrum of FIG. 3.
  • Example 11 Characterization of Acryloyl-Based Bipolymers' (ABB-1), (ABB-2), (ABB-3), and (ABB-4) and Acryloyl-Based Terpolymer 's (ABT-10) Inhibition of Clathrate Hydrate Formation
  • Rocking Cells that is, RC-5 were employed to characterize the ability of acryloyl-based copolymers having structures (ABB-1), (ABB-2), (ABB-3), (ABB-4), and (ABT-10) to inhibit clathrate hydrate formation.
  • the RC-5 included five Hastelloy cells (PSL Systemtechnik Gmbh, Osterode am Harz, Germany) capable of operating under high pressure (that is, up to 200 bars) and in sour gas conditions.
  • the five Hastelloy cells of the RC-5 were immersed in a temperature controlled bath containing ethylene glycol and water. During operation, the RC-5 was rocked to achieve mixing of the reactant slurry.
  • the volume of the Hastelloy cell with a mixing ball was about 30 mL.
  • the RC-5 enabled formation of natural gas clathrate hydrates under simulated operating conditions to test the effectiveness of the acryloyl-based copolymers having structures (ABB-1), (ABB-2), (ABB-3), (ABB-4), and (ABT-10). Data acquisition was completed with WinRC software to measure the pressure and temperature with time in each of the five Hastelloy cells.
  • each of the five Hastelloy cells was charged with about 10 mL of an acryloyl-based copolymer formulation.
  • the 10 mL acryloyl-based copolymer formulation included an acryloyl-based copolymer (about 0.105 g), a solvent (about 0.195 g monoethylene glycol, that is, MEG), and brine (about 9.7 g), as set forth in Table 2.
  • the five Hastelloy cells were charged with a natural gas for one hour until equilibrium was reached, as described in Table 3, that is, a natural gas was added to the five Hastelloy cells, to a pressure of about 140 bars at 21 °C.
  • the brine included an aqueous solution of chloride anions, sodium cations, acetic acid, formic acid, and conjugate bases as set forth in Table 2: Table 2: Brine
  • each of the five Hastelloy cells were charged with 10 mL of an acryloyl-based copolymer formulation including acryloyl-based copolymers having structures (ABB- 1), (ABB -2), (ABB-3), (ABB -4), and (ABT-10) and the brine of Table 2.
  • Each acryloyl-based copolymer structure was tested separately, that is, two different acryloyl-based copolymer structures were not paired together in a single test.
  • the five Hastelloy cells were charged with a natural gas, as described in Table 3, to a pressure of about 140 bars at 21 °C. Referencing FIG.
  • the RC-5 was then programmed to change temperature at three operation stages as set forth generally in Table 4. More specifically, the RC-5 was programmed to change temperature at three operation stages, where Stage 1 was from between about 0 to 1500 minutes, Stage 2 was from about 1500 to 3000 minutes, and Stage 3 was from about 3000 to 32000 minutes.
  • the three-phase equilibrium temperature (that is, liquid, vapor, and hydrate) of clathrate hydrates in the natural gas composition of Table 3 was calculated via methods known to those of ordinary skill in the art.
  • the calculated equilibrium curve of hydrate formation showed the three-phase equilibrium temperature of about 18.6 °C at 140 bars.
  • the pressure changes for liquid, vapor, and hydrate phases were accounted for by employing a mass balance of the natural gas composition so that pressure changes were accurately attributed to clathrate hydrate formation.
  • the ability of acryloyl-based copolymers to inhibit clathrate hydrate formation was evaluated by assessing the pressure during each of the operation stages at the various subcooling temperatures, where a stable pressure was determined to be indicative of clathrate hydrate inhibition.
  • the acryloyl-based bipolymer having structure (ABB-1) was an effective inhibitor of clathrate hydrate formation at both a first subcooling temperature of 4.0 °C and a second subcooling temperature of 5.6 °C.
  • the acryloyl-based terpolymer having structure (ABT-10) was an effective inhibitor of clathrate hydrate formation at both a first subcooling temperature and a second subcooling temperature.
  • the acryloyl-based bipolymers having structures (ABB-5), (ABB-6), and (ABB-7) were effective inhibitors of clathrate hydrate formation at a first subcooling temperature of 4.0 °C.
  • the acryloyl-based bipolymer having structure (ABB-8) was an effective inhibitor of clathrate hydrate formation at a first subcooling temperature of 4.0 °C and at a second subcooling temperature of 5.6 °C.
  • minimal clathrate hydrate was formed at a third subcooling temperature 10.5 °C in the presence of acryloyl-based bipolymer having structure (ABB-8).
  • PVcap was not an effective inhibitor of clathrate hydrate formation at any subcooling temperature.
  • the acryloyl-based bipolymer having structure (ABB-9) was an effective inhibitor of clathrate hydrate formation at a first subcooling temperature of 4.0 °C, a second subcooling temperature of 5.6 °C, and a third subcooling temperature of 10.5 °C.
  • the acryloyl-based bipolymer having structure (ABB-15) was an effective inhibitor of clathrate hydrate formation at a first subcooling temperature of 4.0 °C and at a second subcooling temperature of 5.6 °C.
  • Example 14 Characterization of Ability of Acryloyl-Based Homopolymers having Structures (ABH-11 )-(ABH-14) to Inhibit Clathrate Hydrate Formation
  • (ABH-11) was synthesized by adding ABCVA (about 0.35 g, 1.25 mmol) to a solution having a monomeric repeating unit of structure (Ml) (about 72 mmol):
  • (ABH-12) was synthesized by adding ABCVA (about 0.35 g, 1.25 mmol) to a solution having a monomeric repeating unit of structure (Ml) (about 72 mmol):
  • (ABH-13) was synthesized by adding ABCVA (about 0.35 g, 1.25 mmol) to a solution having a monomeric repeating unit of structure (Ml) (about 72 mmol):
  • Acryloyl-based bipolymers that is, ABB having General Formula (I) in which R 1 is -(CH 2 ) 2 -0-(CH 2 )2-, R 2 is Q 1 in which R 4 is -(CH 2 ) 5 -, R 3 is not present, x is about 0.5, y is about 0.5, and z is 0, were synthesized.
  • acryloyl-based bipolymers having General Formula (I) were synthesized by adding ABCVA (about 350 milligrams, that is mg, 1.25 mmol) to a solution having a monomeric repeating unit of structure (Ml) (about 36.3 mmol):

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Abstract

L'invention concerne des copolymères répondant à la formule générale (I) : [insérer la formule] dans laquelle R1 et R3 sont choisis parmi des groupes aliphatiques en C4-C7 divalents et des groupes hétéroaliphatiques en C4-C7 divalents, éventuellement substitués par un ou plusieurs groupes aliphatiques en C1-C6, hétéroatomes choisis indépendamment parmi O, N et S, ou une combinaison de ceux-ci, dans laquelle les groupes hétéroaliphatiques en C4-C7 divalents de R1 et R3 comprennent un ou deux hétéroatomes choisis indépendamment parmi O, N et S, et le nombre maximal d'hétéroatomes dans R1 ou R3 est égal à deux, R2 est choisi parmi Q1 et Q2, x est une plage de fraction molaire choisie entre 0,1 et 0,9, y est une plage de fraction molaire choisie entre 0,1 et 0,9, et z est une plage de fraction molaire choisie entre 0 et 0,8, la somme de x, y et z étant égale à 1. L'invention concerne des procédés pour inhiber la formation d'hydrates de clathrate qui comprennent la mise en contact d'un fluide avec au moins un copolymère de formule générale (I).
PCT/US2017/030795 2016-05-06 2017-05-03 Copolymères à base d'acryloyle, terpolymères et leur utilisation en tant qu'inhibiteurs d'hydrates Ceased WO2017192689A1 (fr)

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KR1020187035324A KR102337330B1 (ko) 2016-05-06 2017-05-03 아크릴로일계 공중합체들, 삼원 중합체들 및 수화물 억제제들로서의 용도
SG11201809667VA SG11201809667VA (en) 2016-05-06 2017-05-03 Acryloyl-based copolymers, terpolymers, and use as hydrate inhibitors
EP17723838.3A EP3452526B1 (fr) 2016-05-06 2017-05-03 Copolymères à base d'acryloyle, terpolymères et leur utilisation en tant qu'inhibiteurs d'hydrates
CN201780027848.5A CN109071729B (zh) 2016-05-06 2017-05-03 基于丙烯酰基的共聚物、三元共聚物及作为水合物抑制剂的用途
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JP2019515107A (ja) 2019-06-06
CN109415469A (zh) 2019-03-01
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JP2019515109A (ja) 2019-06-06
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US20200115484A1 (en) 2020-04-16
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US20170320985A1 (en) 2017-11-09
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